WO2023238506A1 - Dispersion liquide ainsi que procédé de fabrication de celle-ci, et procédé de fabrication de stratifié - Google Patents

Dispersion liquide ainsi que procédé de fabrication de celle-ci, et procédé de fabrication de stratifié Download PDF

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WO2023238506A1
WO2023238506A1 PCT/JP2023/015140 JP2023015140W WO2023238506A1 WO 2023238506 A1 WO2023238506 A1 WO 2023238506A1 JP 2023015140 W JP2023015140 W JP 2023015140W WO 2023238506 A1 WO2023238506 A1 WO 2023238506A1
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dispersion
particles
polymer
liquid
manufacturing
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PCT/JP2023/015140
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English (en)
Japanese (ja)
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蔵 藤岡
文 伊藤
創太 結城
渉 笠井
賢太 関川
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Ａｇｃ株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene

Definitions

  • the present invention relates to a method for producing a dispersion containing particles of a tetrafluoroethylene polymer, a dispersion, and a method for producing a laminate.
  • Patent Document 1 describes that by dispersing tetrafluoroethylene polymer particles having an average particle diameter of 60 ⁇ m or less obtained by dry pulverization in an aqueous medium and passing them through a passage of a specific width under a specific pressure (wet jet mill), A method for producing an aqueous dispersion in which finely divided tetrafluoroethylene polymer particles are dispersed has been proposed.
  • Tetrafluoroethylene-based polymers have low surface tension, so their particles have low dispersibility. If the dispersion is aqueous, the versatility of the equipment required to use it and the selectivity of the substrate to be coated etc. are high, but the dispersion tends to foam easily, reducing its ease of handling. It's easy to do.
  • the method of Patent Document 1 is not only limited in the types of dispersions that can be applied, but also has low productivity. In particular, since particles in an aqueous medium are collided at high speed under high shear conditions to obtain particles on the order of several micrometers, coarse particles may be generated in the resulting aqueous dispersion, and such coarse particles are likely to cause foaming. .
  • the present inventors have found that when a liquid composition containing tetrafluoroethylene polymer particles and a liquid dispersion medium and having a liquid density within a specific range is treated with a wet bead mill, the formation of coarse particles is suppressed and the dispersion state and dispersion stability are improved. It was found that a dispersion with excellent properties, suppressed foaming, and easy to handle could be obtained.
  • the object of the present invention is to provide a method for producing a dispersion containing tetrafluoroethylene polymer particles and a liquid dispersion medium, which suppresses the formation of coarse particles and has excellent dispersion stability and handling properties, and from the dispersion.
  • the present invention provides a method for producing a laminate having a formed polymer layer, and a method for producing the laminate.
  • the present invention has the following aspects.
  • a liquid composition containing particles of a tetrafluoroethylene polymer and a liquid dispersion medium having a liquid density of 1.15 to 1.5 g/cm 3 is processed using a wet bead mill to obtain a solution of the tetrafluoroethylene polymer.
  • a method for producing a dispersion liquid which obtains a dispersion liquid containing particles.
  • the dispersion obtained by the method according to any one of [1] to [11] is placed on the surface of a base material and heated to form a polymer layer containing the tetrafluoroethylene polymer, and A method for producing a laminate, the method comprising obtaining a laminate having a base material layer made of a base material and the polymer layer in this order.
  • the base material contains at least two types of diamine units derived from 1,4-bis(4-aminophenoxy)benzene and 4,4'-diaminobenzanilide, and has a dielectric constant of 3.0 at 5.8 GHz. 5 or less, a dielectric loss tangent of 0.006 or less, a water absorption rate of 1.2% or less, and a linear expansion coefficient of 2 to 18 ppm/°C at 50 to 200°C, the manufacturing method according to [14].
  • a dispersion liquid can be obtained in which the formation of coarse particles is suppressed and excellent dispersion stability and handling properties are achieved.
  • Such a dispersion can be used to produce molded products such as coatings that have excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent) based on the tetrafluoroethylene polymer, and that have particularly excellent surface appearance.
  • a laminate having a polymer layer formed from the dispersion can be formed.
  • Average particle diameter (D50) is the volume-based cumulative 50% diameter of particles or fillers determined by laser diffraction/scattering method. That is, the particle size distribution is measured by a laser diffraction/scattering method, a cumulative curve is determined with the total volume of the particle population as 100%, and the particle diameter is the point on the cumulative curve where the cumulative volume becomes 50%.
  • the D50 of particles or fillers is determined by dispersing the particles in water and analyzing the particles using a laser diffraction/scattering method using a laser diffraction/scattering particle size distribution analyzer (LA-920 measuring instrument, manufactured by Horiba, Ltd.) .
  • Average particle diameter (D90) is the volume-based cumulative 90% diameter of particles, which is determined in the same manner as D50.
  • the specific surface area of particles or fillers is a value calculated by measuring particles by gas adsorption (constant volume method) BET multi-point method, and is determined using NOVA4200e (manufactured by Quantachrome Instruments).
  • Melting temperature is the temperature corresponding to the maximum value of the melting peak of the polymer as measured by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • Glass transition point (Tg)” is a value measured by analyzing a polymer using a dynamic mechanical analysis (DMA) method.
  • Viscosity is determined by measuring the composition using a B-type viscometer at 25° C.
  • the "thixotropic ratio” is a value calculated by dividing the viscosity ⁇ 1 of the composition measured at a rotation speed of 30 rpm by the viscosity ⁇ 2 measured at a rotation speed of 60 rpm. Each viscosity measurement was repeated three times, and the average value of the three measurements was taken.
  • the "surface tension” of a solvent or solution is a value measured by the Wilhelmy method at 25° C. using a surface tension meter.
  • the "HLB (Hydrophilic-Lipophilic Balance) value” of a surfactant is a value defined by the following calculation formula using the Griffin method.
  • a “unit” in a polymer means an atomic group based on the monomer formed by polymerization of the monomer.
  • the unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of said unit is converted into another structure by processing the polymer.
  • a unit based on monomer a will also be simply referred to as a "monomer a unit.”
  • the manufacturing method of the present invention (hereinafter also referred to as “this method”) is a tetrafluoroethylene-based polymer (hereinafter also referred to as "F polymer”) having a liquid density of 1.15 to 1.5 g/ cm3 .
  • F polymer tetrafluoroethylene-based polymer
  • a liquid composition containing particles of (hereinafter also referred to as “F particles”) and a liquid dispersion medium is processed in a wet bead mill to obtain a dispersion containing particles of the tetrafluoroethylene polymer.
  • a dispersion liquid with excellent dispersion stability and handling properties can be obtained.
  • Molded products such as coating films (polymer layers) formed from such dispersions have excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent) based on the tetrafluoroethylene polymer. , especially its surface appearance is excellent.
  • excellent surface appearance refers to excellent surface smoothness such as "less roughness on the surface", or visual recognition or analysis such as "no streaks, cracks, defects, etc. on the surface”. It includes any appearance that is excellent as observed by equipment.
  • the reason why the dispersion obtained by this method suppresses the formation of coarse particles, has excellent dispersion stability, suppresses foaming, and has excellent handling properties is not necessarily clear, but it is thought to be as follows.
  • the F polymer has a low surface tension, is difficult to wet with a liquid dispersion medium, and is easily fibrillated and deteriorated in quality. Therefore, in a dispersion containing F particles, it is difficult to adjust the wettability of the F particle surface and the cohesiveness of the F particles in a well-balanced manner. Therefore, the dispersion stability is reduced due to the formation of coarse particles in the liquid, the handling properties are reduced due to the generation of bubbles, and the coating film (polymer layer) formed from the dispersion is likely to have poor appearance or defects.
  • the wet bead milling process in this method can be regarded as a so-called dispersion process.
  • the F polymer in the present invention is a polymer containing units based on tetrafluoroethylene (hereinafter also referred to as "TFE") (hereinafter also referred to as “TFE units”).
  • TFE tetrafluoroethylene
  • the F polymer may be thermofusible or non-thermofusible.
  • thermofusible polymer means a polymer that exists at a temperature at which the melt flow rate is 1 to 1000 g/10 minutes under a load of 49N.
  • a non-thermofusible polymer means a polymer that does not have a temperature at which the melt flow rate is 1 to 1000 g/10 minutes under a load of 49N.
  • the melting temperature of the heat-melting F polymer is preferably 180°C or higher, more preferably 200°C or higher.
  • a molded article such as a coating film (polymer layer) formed from the present dispersion tends to have excellent heat resistance.
  • the melting temperature of the F polymer is preferably 325°C or lower, more preferably 320°C or lower.
  • the melting temperature of the F polymer is preferably 180°C to 325°C, more preferably 200°C to 325°C, and even more preferably 200°C to 320°C, from the viewpoint that the above-mentioned mechanism of action is more likely to occur.
  • the glass transition point of the F polymer is preferably 50°C or higher, more preferably 75°C or higher.
  • the glass transition point of the F polymer is preferably 150°C or lower, more preferably 125°C or lower.
  • the fluorine content of the F polymer is preferably 70% by mass or more, more preferably 72 to 76% by mass.
  • the surface tension of the F polymer is preferably 16 to 26 mN/m.
  • the surface tension of F polymer can be measured by placing droplets of a wet tension test mixture (manufactured by Wako Pure Chemical Industries, Ltd.) specified in JIS K 6768 on a flat plate made of F polymer. .
  • F polymers include polytetrafluoroethylene (PTFE), polymers containing TFE units and units based on ethylene (ETFE), polymers containing TFE units and units based on propylene, TFE units and perfluoro(alkyl vinyl ether) (PAVE)
  • PTFE polytetrafluoroethylene
  • ETFE ethylene
  • PAVE perfluoro(alkyl vinyl ether)
  • a polymer (PFA) containing a unit based on (PAVE unit), a polymer (FEP) containing a TFE unit and a unit based on hexafluoropropylene are preferred, PFA or FEP is more preferred, and PFA is even more preferred.
  • F polymer one type of these polymers may be used alone, two or more types may be used in combination, and units based on other comonomers may also be included.
  • PTFE examples include low molecular weight PTFE and modified PTFE.
  • CF 2 CFOCF 3
  • CF 2 CFOCF 2 CF 3
  • the F polymer preferably has an oxygen-containing polar group, more preferably a hydroxyl group-containing group or a carbonyl group-containing group, and even more preferably a carbonyl group-containing group.
  • the dispersion obtained by this method tends to have excellent dispersion stability and handling properties.
  • molded products such as coating films (polymer layers) formed from such dispersions have excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent), and their surface appearance.
  • the hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, and more preferably -CF 2 CH 2 OH or -C(CF 3 ) 2 OH.
  • the carbonyl group-containing group examples include a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH 2 ), an acid anhydride residue (-C(O)OC(O)-), Imide residues (-C(O)NHC(O)-, etc.) or carbonate groups (-OC(O)O-) are preferred, and acid anhydride residues are more preferred.
  • the number of oxygen-containing polar groups in the F polymer is preferably 10 to 5,000, more preferably 100 to 3,000 per 1 ⁇ 10 6 carbon atoms in the main chain of the F polymer. preferable. Note that the number of oxygen-containing polar groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133.
  • the oxygen-containing polar group may be contained in a unit based on a monomer in the F polymer, or may be contained in a terminal group of the main chain of the F polymer, with the former being preferred.
  • Examples of the latter embodiment include an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F polymer obtained by subjecting the F polymer to plasma treatment or ionizing radiation treatment.
  • the F polymer is preferably a polymer having carbonyl group-containing groups, including TFE units and PAVE units, and includes units based on monomers having TFE units, PAVE units and carbonyl group-containing groups, and for the total units: More preferably, the polymer contains 90 to 99 mol%, 0.99 to 9.97 mol%, and 0.01 to 3 mol% of these units in this order. Specific examples of such F polymers include the polymers described in International Publication No. 2018/16644.
  • the monomer having a carbonyl group-containing group is preferably itaconic anhydride, citraconic anhydride, or 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), and more preferably NAH.
  • the D50 of the F particles is preferably less than 10 ⁇ m, more preferably 1 ⁇ m or more and less than 10 ⁇ m.
  • the F particles may be solid particles or non-hollow particles.
  • the F particles may be secondary particles formed from nanometer-order fine particles.
  • the D50 of the F particles is preferably 1.0 ⁇ m or more, more preferably 1.5 ⁇ m or more.
  • D50 of the F particles is preferably 6 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the D90 of the F particles is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less.
  • the specific surface area of the F particles is preferably 1 to 25 m 2 /g, more preferably 6 to 15 m 2 /g.
  • the dispersion obtained by this method tends to have excellent dispersion stability and handling properties.
  • molded products such as coating films (polymer layers) formed from such dispersions have excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent), and their surface appearance. Cheap.
  • the specific surface area of the F particles is within the above range, the surface of the F particles is easily wetted by a liquid dispersion medium or a water-soluble solvent having a surface tension in a specific range described below, and aggregates of F particles are easily disintegrated. It is thought that the mechanism of action described above is more likely to occur.
  • the F particles are particles containing F polymer, and are preferably composed of F polymer. More preferably, the F particles are particles of a heat-melting F polymer having an oxygen-containing polar group and having a melting temperature of 200 to 325°C. In this case, the above-mentioned mechanism of action is more fully expressed, and aggregation of F particles is more likely to be suppressed.
  • the F particles may contain a resin or an inorganic compound other than the F polymer, or may form a core-shell structure in which the F polymer is the core and the shell is a resin or inorganic compound other than the F polymer.
  • a core-shell structure may be formed in which the shell is made of a resin other than F polymer or an inorganic compound is made of a core.
  • examples of the resin other than the F polymer include aromatic polyester, polyamideimide, polyimide, and maleimide
  • examples of the inorganic compound include silica and boron nitride.
  • F particles may be used, or two or more types may be used. Further, the F particles may be used in combination with particles of a non-thermofusible tetrafluoroethylene polymer.
  • the F particles particles of a heat-melting F polymer having a melting temperature of 200 to 325°C are preferable, and particles of a heat-melting F polymer having a melting temperature of 200 to 325°C and having an oxygen-containing polar group are more preferable.
  • particles of the non-thermo-fusible tetrafluoroethylene polymer particles of non-thermo-fusible PTFE are preferable.
  • the dispersibility of the dispersion obtained by this method is improved due to the balance between the agglomeration inhibiting effect of the heat-fusible F polymer particles and the retention effect of the fibrillation of the non-thermo-fusible tetrafluoroethylene polymer. It's easy to do.
  • the electrical properties of the non-thermofusible tetrafluoroethylene polymer tend to be highly expressed.
  • the liquid dispersion medium constituting the liquid composition is preferably at least one selected from the group consisting of water, amides, ketones, and esters.
  • amides include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy -N,N-dimethylpropanamide, N,N-diethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone.
  • ketone examples include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone.
  • esters include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, ⁇ -butyrolactone, ⁇ - Includes valerolactone.
  • the liquid dispersion medium is preferably miscible with water and a water-soluble solvent having a surface tension within a specific range, which will be described later, and it is more preferable that the liquid dispersion medium is water.
  • the liquid composition may further contain a surfactant.
  • a surfactant nonionic surfactants are preferred.
  • the nonionic surfactant include glycol surfactants, acetylene surfactants, silicone surfactants, and fluorine surfactants.
  • Specific examples of nonionic surfactants include the "Ftergent” series (manufactured by Neos), the “Surflon” series (manufactured by AGC Seimi Chemical), the "Megafac” series (manufactured by DIC), and the "Unidyne” series (manufactured by DIC).
  • nonionic surfactants having a hydroxyl group in the hydrophilic site are preferred, and silicone surfactants with an HLB value of 10 or more are preferred, and have a polyoxyalkylene structure as the hydrophilic site and a polydimethylsiloxane structure as the hydrophobic site.
  • polyoxyalkylene-modified dimethylsiloxane is more preferred.
  • the polyoxyalkylene-modified dimethylsiloxane may have a polydimethylsiloxane unit (-(CH 3 ) 2 SiO 2/2 -) in the main chain or a polydimethylsiloxane unit in the side chain. It may also have polydimethylsiloxane units in both the main chain and the side chain.
  • Polyoxyalkylene-modified polydimethylsiloxane contains dimethylsiloxane units in the main chain and has an oxyalkylene group in the side chain, or polyoxyalkylene-modified polydimethylsiloxane contains dimethylsiloxane units in the main chain and has an oxyalkylene group in the side chain.
  • Polyoxyalkylene-modified polydimethylsiloxane having an oxyalkylene group is preferred.
  • the oxyalkylene group contained in the polyoxyalkylene-modified dimethylsiloxane may consist of only one type of oxyalkylene group, or may consist of two or more types of oxyalkylene groups. In the latter case, different types of oxyalkylene groups may be connected in a random manner or in a block manner.
  • One kind of surfactant may be used, or two or more kinds of surfactants may be used. Further, it is preferable to use the surfactant so that the content of the surfactant in the dispersion obtained by this method is in the range of 1 to 15 parts by mass, and 3 to 10 parts by mass, based on 100 parts by mass of F particles. It is more preferable to use the range.
  • the liquid composition may further contain a viscosity modifier.
  • a viscosity modifier is contained, the dispersion state and dispersion stability of the dispersion obtained by this method are likely to be improved. In addition, the rheological properties are improved, and the handling properties such as film-forming properties of the dispersion obtained by this method are easily improved, and it is easier to form a thick polymer layer.
  • the viscosity modifier is preferably at least one selected from the group consisting of polar vinyl polymers and polysaccharides.
  • a polar vinyl polymer is a vinyl polymer that has a polar functional group in the main chain or side chain of the polymer, and examples of the polar functional group include an ether bond, an ester bond, an amide bond, an imide bond, a thioether bond, and a sulfide bond. Examples include bond, disulfide bond, carbonyl group-containing group, hydroxyl group-containing group, thiol group, sulfide group, sulfonyl group, sulfoxyl group, amino group, and amide group.
  • Examples of the polar vinyl polymer include vinyl alcohol polymers such as polyvinyl alcohol, vinyl pyrrolidone polymers such as polyvinylpyrrolidone, acrylic acid polymers such as polyacrylic acid, and carboxyvinyl polymers such as carboxyvinyl polymer.
  • vinyl alcohol polymers include polyvinyl alcohol, polyvinyl acetate, partially acetylated or partially acetalized polyvinyl alcohol, and copolymers of vinyl alcohol, vinyl butyral, and vinyl acetate.
  • vinyl alcohol-based polymers include the "S-LEC (registered trademark) B” series, “S-LEC (registered trademark) K (KS)” series, and “S-LEC (registered trademark) SV” series (all manufactured by Sekisui Chemical Co., Ltd.). )” and “Movitar (registered trademark)” series (manufactured by Kuraray Co., Ltd.).
  • acrylic acid polymers include salts of polyacrylic acid such as polyacrylic acid, sodium polyacrylate, sodium acrylic acid/maleic acid copolymer, sodium acrylic acid/sulfonic acid monomer copolymer, polymethyl acrylate, and polyacrylic acid.
  • examples include polyacrylates such as ethyl acrylate, poly- ⁇ -haloacrylates, poly- ⁇ -cyanoacrylates, and polyacrylamides.
  • Polysaccharides include glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, fructan, chitin, xanthan gum, guar gum, casein, gum arabic, gelatin, agaropectin, arabinan, curdlan, callose, carboxymethyl starch, chitosan, and quince.
  • Seed glucomannan, gellan gum, tamarin seed gum, dextran, nigeran, hyaluronic acid, pustulan, funolan, pectin, porphyran, laminaran, lichenan, carrageenan, alginic acid, tragacanth gum, alkasi gum, locust bean gum and the like.
  • nonionic polysaccharides are preferred, glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, fructan, and chitin are preferred, and cellulose is more preferred.
  • Examples of cellulose include cellulose ethers such as alkylcellulose, carboxyalkylcellulose, hydroxyalkylcellulose, and hydroxyalkylalkylcellulose.
  • Examples of the alkylcellulose include methylcellulose and ethylcellulose.
  • Examples of carboxyalkylcellulose include carboxymethylcellulose.
  • Examples of hydroxyalkylcellulose include hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and the like.
  • Examples of the hydroxyalkylalkylcellulose include hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylethylcellulose, and hydroxyethylethylmethylcellulose. Among these, hydroxyalkylcellulose or hydroxyalkylalkylcellulose is preferred, hydroxyalkylcellulose is more preferred, and hydroxyethylcellulose is even more preferred.
  • the weight average molecular weight of the cellulose ether is preferably 1,000 to 10,000. Note that the weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a differential refractive index detector.
  • GPC gel permeation chromatography
  • Specific examples of cellulose ether include the "Sunrose (registered trademark)” series (manufactured by Nippon Paper Industries), the “Metrose (registered trademark)” series (manufactured by Shin-Etsu Chemical Co., Ltd.), and the "HEC CF grade” (manufactured by Sumitomo Seika Chemical Co., Ltd.). (manufactured by).
  • the dispersion obtained by this method contains a viscosity modifier, at least one selected from the group consisting of acrylic acid polymers, vinyl alcohol polymers, and cellulose is preferred among the above.
  • the average molecular weight of the viscosity modifier is preferably 3,000 or more, more preferably 10,000 or more, even more preferably 100,000 or more, and particularly preferably 300,000 or more.
  • the average molecular weight of the viscosity modifier is preferably 1,000,000 or less, more preferably 500,000 or less. In this case, the dispersion obtained by this method tends to have excellent physical properties such as dispersion stability.
  • the viscosity modifier is water-soluble.
  • the thermal decomposition temperature of the viscosity modifier is preferably 150°C or higher, more preferably 200°C or higher.
  • the thermal decomposition temperature of the viscosity modifier is preferably 320°C or lower, more preferably 300°C or lower.
  • the thermal decomposition temperature is preferably below the melting temperature of the F polymer.
  • the viscosity modifier tends to have an excellent effect as a binder, and the viscosity modifier does not easily remain in the molded product formed from the dispersion obtained by this method, so that the molded product has poor physical properties such as electrical properties. Easy to excel.
  • the content of the viscosity modifier When containing a viscosity modifier, its content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total mass of the liquid composition.
  • the content of the viscosity modifier is preferably 30% by mass or less, more preferably 10% by mass or less, based on the total mass of the liquid composition.
  • the ratio of the content of the viscosity modifier to the content of F particles in the liquid composition is preferably 0.001 or more, and more preferably 0.003 or more.
  • the content ratio is preferably 0.05 or less, more preferably 0.03 or less, and even more preferably 0.01 or less.
  • the liquid composition may further contain a water-soluble solvent having a surface tension of 20 to 30 mN/m.
  • the water-soluble solvent having a surface tension of 20 to 30 mN/m is preferably a compound that is liquid at 25°C under atmospheric pressure and has a boiling point of 160°C or lower, and preferably a compound having a boiling point of 120°C or lower. is more preferable.
  • a water-soluble solvent is azeotropic with water.
  • a water-soluble solvent means a solvent whose solubility in water is 100 g/L or more. One type of water-soluble solvent may be used, or two or more types may be used.
  • the water-soluble solvent is preferably a monool having 1 to 6 carbon atoms, such as methanol (23 mN/m), ethanol (23 mN/m), 1-propanol (24 mN/m), 2-propanol (22 mN/m), 1-butanol (25 mN/m), 2-butanol (24 mN/m), isobutanol (23 mN/m), 1-methoxy-2-propanol (26 mN/m), 2-propoxy-ethanol (27 mN/m), 1-propoxy-2-propanol (25 mN/m) and 2-ethoxyethanol (26 mN/m) are more preferred, and ethanol is even more preferred.
  • the numerical value in parentheses is the surface tension of each monol.
  • a liquid composition containing F particles and a liquid dispersion medium having a liquid density of 1.15 to 1.5 g/cm 3 is processed in a wet bead mill to obtain a dispersion containing F particles. It is preferable to prepare a liquid composition by mixing F polymer powder and a liquid dispersion medium.
  • the F polymer powder is an aggregate of F particles, and may be an aggregate of F particles themselves, or may be an aggregate of some F particles aggregated.
  • the F particles and the liquid dispersion medium may be mixed all at once or in multiple batches.
  • surfactant, viscosity modifier, and water-soluble solvent when further mixed into the liquid composition as necessary, they may be mixed all at once when mixing the F particles and the liquid dispersion medium, or each component may be mixed at once. may be sequentially added and mixed, or a mixture of each component dissolved or dispersed in a liquid dispersion medium may be added and mixed to the mixture of F particles and liquid dispersion medium.
  • Mixing devices for preparing liquid compositions include stirring devices equipped with blades such as Henschel mixers, pressure kneaders, Banbury mixers, and planetary mixers, microfluidizers, nanomizers, articulzers, ultrasonic homogenizers, and resolvers.
  • stirring devices equipped with blades such as Henschel mixers, pressure kneaders, Banbury mixers, and planetary mixers, microfluidizers, nanomizers, articulzers, ultrasonic homogenizers, and resolvers.
  • dispersion devices equipped with other mechanisms such as a disperser, a high-speed impeller, a thin film swirl type high-speed mixer, an autorotation-revolution stirrer, and a V-type mixer.
  • a defoaming treatment after the above-mentioned mixing.
  • defoaming treatment include standing treatment, reduced pressure treatment, hot air treatment, and the like.
  • Defoaming treatment may be performed by combining these.
  • a mixing process using the above-mentioned stirring device or dispersion device, and further perform a defoaming process by a vacuum process (vacuum defoaming process).
  • the liquid density of the liquid composition is 1.15 to 1.5 g/cm 3 , preferably 1.24 to 1.42 g/cm 3 , and 1.28 to 1.38 g/cm 3 It is more preferable that When the liquid density of the liquid composition is within the above range, the above-described mechanism of action is likely to be manifested significantly.
  • the liquid dispersion medium in the liquid composition is a liquid dispersion medium containing water as a main component, specifically, when the proportion of water in the liquid dispersion medium is 80 to 100% by mass, the above-mentioned The mechanism of action is likely to be more pronounced.
  • the liquid density of the liquid composition can be adjusted by adjusting the types or amounts of components contained in the liquid composition, or by the above-mentioned standing treatment, reduced pressure treatment, hot air treatment, etc.
  • Specific examples of means for adjusting the liquid density of the liquid composition include means for adjusting the content of F particles in the liquid composition, and more specifically means for adjusting the content to more than 30% by mass.
  • the viscosity of the liquid composition is preferably 100 to 10,000 mPa ⁇ s, more preferably 500 to 3,000 mPa ⁇ s, and even more preferably 1,000 to 5,000 mPa ⁇ s. In this case, the above-mentioned mechanism of action tends to be more pronounced.
  • the viscosity of the liquid composition is preferably controlled by the types of components contained in the liquid composition, particularly by the use of the above-mentioned viscosity modifiers.
  • the surface tension of the liquid composition is preferably 15 to 45 mN/m, more preferably 20 to 35 mN/m, and even more preferably 20 to 30 mN/m. In this case, the above-mentioned mechanism of action tends to be more pronounced.
  • the surface tension of the liquid composition is preferably adjusted by the types of components contained in the liquid composition, particularly by the use of the above-mentioned water-soluble solvent.
  • the bead mill used in this method includes, for example, a hollow cylindrical container filled with beads as a media, and an agitator disposed within the container to agitate the liquid composition and the beads.
  • the agitator for example, one that is arranged coaxially with the container and has a hollow cylindrical shape or an impeller shape can be used.
  • Bead mills include batch type, pass type, circulation type, etc., depending on their operating method.
  • the treatment (dispersion treatment) in this method uses beads with a diameter of 2 mm or less, and is preferably selected from a batch type, pass type, or circulation type bead mill.
  • the liquid composition is sent from a tank to a bead mill, treated in the bead mill, separated from the beads by a bead separation means, and returned to the tank, and repeated until a desired dispersion is obtained.
  • bead separation means include centrifuges, gap separators, separation screens, and the like.
  • the treatment may be performed while cooling the container.
  • a stationary treatment, a reduced pressure treatment, a hot air treatment, etc. may be further performed. Specifically, it is preferable to further perform vacuum degassing treatment.
  • the diameter of the beads is preferably in the range of 0.1 to 10 mm, more preferably in the range of 1 to 5 mm.
  • the material of the beads include zirconia, silica, alumina, glass, and metal.
  • Bead mills include, for example, the vertical type "Alpha Mill” manufactured by Imex, the horizontal type “New Visco Mill NVM type” and “Ultra Visco Mill UVM type”; the "DYNO-MILL” manufactured by WAB, and the Hiroshima Metal & Machinery Company. ⁇ Ultra Aspex Mill'', ⁇ My Mill'' manufactured by Nippon Coke Industry Co., Ltd., and ⁇ Star Mill'' manufactured by Ashizawa Finetech.
  • At least one of a liquid dispersion medium, an aromatic polymer, or an inorganic filler may be further mixed into the dispersion after processing with a wet bead mill.
  • the types of liquid dispersion media that can be mixed are the same as those described above.
  • a molded article such as a coating film (polymer layer) formed from the dispersion tends to have excellent electrical properties and low linear expansion.
  • the shape of the inorganic filler may be spherical, needle-like (fibrous), or plate-like, and specifically, spherical, scale-like, layered, leaf-like, apricot-like, columnar, cock-comb-like, etc. It may be axial, leaf-like, mica-like, block-like, flat-plate-like, wedge-like, rosette-like, mesh-like, or prismatic.
  • inorganic fillers examples include quartz powder, silica, wollastonite, talc, silicon compounds such as silicon nitride, silicon carbide, and mica; nitrogen compounds such as boron nitride and aluminum nitride; aluminum oxide, zinc oxide, titanium oxide, and cerium oxide. , metal oxides such as beryllium oxide, magnesium oxide, nickel oxide, vanadium oxide, copper oxide, iron oxide, silver oxide; carbon fibers; carbon allotropes such as graphite, graphene, carbon nanotubes; metals such as silver and copper; It will be done.
  • One type of inorganic particles may be used, or two or more types may be used in combination.
  • the D50 of the inorganic filler is preferably 0.1 to 50 ⁇ m.
  • the surface of the inorganic filler may be surface-treated with a silane coupling agent.
  • inorganic fillers include silica fillers ("Adma Fine (registered trademark)” series (manufactured by Admatex), "SFP (registered trademark)” series (manufactured by Denka Corporation), “E-SPHERES” series (manufactured by Denka Corporation), ), zinc oxide filler ( ⁇ FINEX (registered trademark)'' series (manufactured by Sakai Chemical Industry Co., Ltd.), etc.), titanium oxide filler ( ⁇ Taipeke (registered trademark)'' series (manufactured by Ishihara Sangyo Co., Ltd.), “JMT (registered trademark)” series (manufactured by Teika Co., Ltd.), talc fillers ("SG” series (manufactured by Nippon Talc Co., Ltd.), etc.), steatite fillers ("BST” series (manufactured by Nippon Talc Co., Ltd.), etc.), nite fillers ("
  • the dispersion obtained by this method further contains an aromatic polymer from the viewpoint of improving the dispersion stability of the F particles.
  • an aromatic polymer may be contained as non-hollow particles, or may be contained dissolved or dispersed in the above-mentioned liquid dispersion medium.
  • the aromatic polymer include polyester resins such as liquid crystalline aromatic polyesters, polyimide resins, polyamideimide resins, epoxy resins, maleimide resins, urethane resins, polyphenylene ether resins, polyphenylene oxide resins, and polyphenylene sulfide resins.
  • At least one aromatic imide polymer selected from the group consisting of aromatic polyimide, aromatic polyamic acid, aromatic polyamideimide, and precursors of aromatic polyamideimide is more preferred.
  • the aromatic polymer is included as a varnish dissolved in a liquid dispersion medium.
  • aromatic imide polymers include the "Yupia-AT” series (manufactured by UBE), the “Neoprim (registered trademark)” series (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the “Spixeria (registered trademark)” series (manufactured by Somar). ), “Q-PILON (registered trademark)” series (manufactured by P.I.
  • the content of the aromatic polymer relative to the F particles is preferably 1 to 25% by mass.
  • the dispersion obtained by this method further contains a thixotropic agent, an antifoaming agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, and a coloring agent.
  • a conductive agent, a mold release agent, a flame retardant, and other various additives may be added.
  • the present invention provides a dispersion liquid containing F particles and a liquid dispersion medium (hereinafter referred to as " (also referred to as “this dispersion liquid”).
  • concentration of particles with a particle size of 60 ⁇ m or more as measured by a particle counter in this dispersion is 500 particles/ml from the viewpoint of preventing streaks, cracks, and defects from occurring on the surface of molded products such as layers formed from this dispersion. It is preferably less than 200 pieces/ml, and more preferably less than 200 pieces/ml. Moreover, it is preferable that the lower limit is 1 piece/ml. Details of the F polymer, F particles, and liquid dispersion medium in this dispersion are the same as those described above in the explanation of this method.
  • the dispersion is produced by the method.
  • the present dispersion liquid is preferably obtained by processing the above-described liquid composition containing F particles and a liquid dispersion medium with a liquid density of 1.15 to 1.5 g/cm 3 using a wet bead mill. .
  • This dispersion has excellent dispersion stability and handling properties.
  • molded products such as coating films (polymer layers) formed from this dispersion have excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent) based on the F polymer. Its surface appearance is excellent.
  • the content of F particles in this dispersion is preferably more than 30% by mass from the viewpoints of making it easier to form a thick layered molded product and imparting high physical properties to the F polymer in the resulting molded product. is preferable, and more preferably 35% by mass or more.
  • the content of F particles is preferably 75% by mass or less, more preferably 60% by mass or less.
  • the content range of the tetrafluoroethylene polymer particles is preferably more than 30% by mass and 75% by mass or less, more preferably 35% by mass or more and 60% by mass or less.
  • the content of the liquid dispersion medium in the present dispersion is preferably 25% by mass or more, more preferably 40% by mass or more.
  • the content of the liquid dispersion medium is preferably less than 70% by mass, more preferably 65% by mass or less. Further, the content of the liquid dispersion medium in the present dispersion is preferably 60 to 180% by mass based on the content of F particles.
  • This dispersion may contain a surfactant, a viscosity modifier, a water-soluble solvent, an aromatic polymer, an inorganic filler, and various additives as necessary. Details of the surfactant, viscosity modifier, water-soluble solvent, aromatic polymer, inorganic filler, and various additives are the same as described above.
  • the content thereof is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, per 100 parts by mass of F particles. Furthermore, when the dispersion liquid contains the above-mentioned surfactant, the content thereof is preferably 1 to 10% by mass based on the content of F particles.
  • the content is preferably 0.1% by mass or more, more preferably 1% by mass or more.
  • the content of the water-soluble solvent is preferably 10% by mass or less, and preferably 5% by mass or less.
  • the content thereof is preferably 1 to 10% by mass based on the content of the F particles.
  • Such a water-soluble solvent is also considered to play the role of an antifoaming agent, such as a foam suppressing effect or a foam breaking effect.
  • the viscosity of the present dispersion is preferably 10 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more.
  • the viscosity of the present dispersion is preferably 10,000 mPa ⁇ s or less, more preferably 3,000 mPa ⁇ s or less.
  • the present dispersion has excellent coating properties and is easy to form molded articles such as coating films (polymer layers) having arbitrary thicknesses. Further, the present dispersion having a viscosity within this range tends to exhibit the physical properties of the F polymer to a high degree in molded articles formed therefrom.
  • the thixotropic ratio of this dispersion is preferably 1.0 to 3.0. In this case, the present dispersion has excellent coating properties and homogeneity, and can easily produce denser molded products. These liquid physical properties are likely to be improved when the present dispersion contains the above-mentioned viscosity modifier.
  • the pH of the dispersion is more preferably 8 to 10 from the viewpoint of improving long-term storage properties.
  • the pH of the dispersion can be controlled by a pH adjuster (amine, ammonia, citric acid, etc.) or a pH buffer (tris(hydroxymethyl)aminomethane, ethylenediaminetetraacetic acid, ammonium bicarbonate, ammonium carbonate, ammonium acetate, etc.). Can be adjusted.
  • the dielectric constant of the molded article formed from the dispersion obtained by this method is preferably 2.4 or less, more preferably 2.0 or less. Moreover, it is preferable that the dielectric constant is more than 1.0.
  • the dielectric loss tangent of the molded product is preferably 0.0022 or less, more preferably 0.0020 or less. Moreover, it is preferable that the dielectric loss tangent is more than 0.0010.
  • the thermal conductivity of the molded product is preferably 1 W/m ⁇ K or more, more preferably 3 W/m ⁇ K or more.
  • the dispersion obtained by this method is subjected to a molding method such as extrusion into a sheet shape, a molded product such as a sheet containing the F polymer can be formed.
  • the sheet obtained by extrusion may be further subjected to press molding, calendar molding, etc. and then cast.
  • the sheet is further heated to remove the liquid dispersion medium and sinter the F polymer.
  • the thickness of the sheet formed from the dispersion obtained by this method is preferably 1 to 1000 ⁇ m. Suitable ranges of the dielectric constant, dielectric loss tangent, and thermal conductivity of the sheet are the same as the ranges of the dielectric constant, dielectric loss tangent, and thermal conductivity of the molded article, respectively.
  • the thermal conductivity of the sheet means the thermal conductivity in the in-plane direction of the sheet.
  • the coefficient of linear expansion of the sheet is preferably 100 ppm/°C or less, more preferably 80 ppm/°C or less.
  • the lower limit of the linear expansion coefficient of the sheet is preferably 30 ppm/°C.
  • the linear expansion coefficient means a value obtained by measuring the linear expansion coefficient of a test piece in the range of 25° C. or higher and 260° C. or lower according to the measurement method specified in JIS C 6471:1995.
  • a laminate can be formed by laminating such sheets on a base material.
  • Examples of the method for manufacturing the laminate include a method of extrusion molding the dispersion obtained by this method onto the base material, a method of thermocompression bonding the sheet and the base material, and the like.
  • the base material examples include metal substrates such as metal foils of copper, nickel, aluminum, titanium, and alloys thereof; polyimide, polyamide, polyetheramide, polyphenylene sulfide, polyallyletherketone, polyamideimide, liquid crystalline polyester,
  • metal substrates such as metal foils of copper, nickel, aluminum, titanium, and alloys thereof
  • films of heat-resistant resin such as tetrafluoroethylene polymer
  • prepreg substrates precursor of fiber-reinforced resin substrates
  • ceramic substrates such as silicon carbide, aluminum nitride, and silicon nitride
  • glass substrates examples include glass substrates.
  • the shape of the base material examples include a planar shape, a curved shape, and an uneven shape. Further, the shape of the base material may be any of foil, plate, film, and fiber. The ten-point average roughness of the surface of the base material is preferably 0.01 to 0.05 ⁇ m. The surface of the base material may be surface-treated with a silane coupling agent or may be plasma-treated.
  • Such silane coupling agents include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, -A silane coupling agent having a functional group such as isocyanatepropyltriethoxysilane is preferred.
  • the peel strength between the sheet and the base material is preferably 10 to 100 N/cm or more.
  • the dielectric constant of the polyimide film at 5.8 GHz is preferably 3.5 or less, more preferably 3.4 or less.
  • the dielectric loss tangent of the polyimide film at 5.8 GHz is preferably 0.006 or less, more preferably 0.0055 or less.
  • the dielectric constant and dielectric loss tangent can be measured, for example, with a perturbation method dielectric constant measuring device CP521 (for 5.8 GHz) manufactured by Agilent Technologies Co., Ltd./Kanto Denshi Application Development Co., Ltd. connected to a network analyzer 8722A/C/D.
  • the water absorption rate of the polyimide film is preferably 1.2% or less, more preferably 1.1% or less.
  • the water absorption rate is determined by, for example, cutting a polyimide film into a 6 cm diameter circle, measuring the mass (dry mass: W 0 ) after heat-treating it at 200° C. for 1 hour, and then leaving it in distilled water for 1 day to absorb water.
  • the film mass (W 1 ) after water absorption is measured and calculated using the following formula.
  • Water absorption rate (%) (W 1 - W 0 )/W 0 ⁇ 100
  • the linear expansion coefficient of the polyimide film at 50 to 200°C is preferably 2 to 18 ppm/°C, more preferably 4 to 16 ppm/°C.
  • the coefficient of linear expansion can be measured, for example, using a thermomechanical analyzer such as TMA-50 manufactured by Shimadzu Corporation, in a measurement temperature range of 50 to 200° C. and under heating conditions of 10° C./min. Specifically, with a load of 0.25N, the temperature was first raised from 35°C to 230°C at a rate of 10°C/min, then held at the same temperature for 5 minutes, and then lowered to 35°C at a rate of 10°C/min and maintained at the same temperature. After holding for 30 minutes, the temperature was raised again to 230°C at a rate of 10°C/min, and the linear expansion coefficient was calculated by averaging the data from 50 to 200°C during the second heating.
  • the storage modulus of the polyimide film at 360°C is preferably 0.1 GPa or more, more preferably 0.15 GPa or more.
  • the storage modulus is measured, for example, using a viscoelasticity device such as DMS EXSTER 6100 manufactured by Hitachi High-Tech Science, in a temperature range of 25 to 400 ° C., heating rate: 2 ° C / min, frequency: 5 Hz, under a nitrogen atmosphere,
  • the value at 360°C is defined as the 360°C storage modulus.
  • the polyimide film as a base material preferably has high yield strength.
  • the stress at 5% strain of the polyimide film is preferably 180 MPa or more, more preferably 210 MPa or more.
  • the stress at 5% strain is preferably 500 MPa or less.
  • the polyimide film used as the base material has resistance to plastic deformation.
  • the stress at 15% strain of the polyimide film is preferably 225 MPa or more, more preferably 245 MPa or more.
  • the stress at 15% strain is preferably 580 MPa or less. If the polyimide film has high yield strength, in particular, low plastic deformability, the absolute value of the coefficient of linear expansion of the laminate can be made sufficiently low, and the occurrence of warping can be more reliably prevented.
  • the tensile modulus of the polyimide film is preferably 5 GPa or more, more preferably 6 GPa or more.
  • the elongation at break of the polyimide film is preferably 20% or more, more preferably 30% or more.
  • the tensile modulus and elongation at break of a polyimide film can be measured using, for example, RTM-250 (manufactured by A&D) under the conditions of sample width: 10 mm, distance between chucks: 50 mm, and tensile speed: 100 mm/min. . In this case, the laminate has excellent handling properties even when heated and cooled during processing.
  • the tensile modulus of the polyimide film is equal to or higher than the above lower limit, the shrinkage of the polymer layer during heating and cooling during processing will be effectively alleviated by the elasticity of the polyimide film, making it difficult for wrinkles to occur in the laminate. , the physical properties (surface smoothness, etc.) of the resulting processed product are likely to improve. This tendency becomes remarkable when the F polymer content in the polymer layer or the thickness of the polymer layer is large. Moreover, if the tensile modulus of the polyimide film is below the above-mentioned upper limit, the flexibility of the laminate is likely to be further increased.
  • Aromatic polyimide is a polyimide containing an aromatic group in its repeating unit structure.
  • a diamine and a carboxylic dianhydride are reacted to synthesize a polyamic acid, and this polyamic acid is synthesized by a thermal imidization method or a chemical imidization method.
  • aromatic polyimides obtained by imidization using a chemical conversion method.
  • the solvent for synthesizing polyamic acid include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.
  • diamines examples include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 4,4'-oxydianiline, 3,3'-oxydianiline, 3,4 '-oxydianiline, 4,4'-diaminodiphenyldiethylsilane, 4,4'-diaminodiphenylsilane, 1,4-diaminobenzene (p-phenylenediamine), 4,4'-bis(4-aminophenoxy) Biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4- aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 3,3'-dia
  • carboxylic dianhydride examples include pyromellitic dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl ) propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis( 3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dian
  • this dispersion is placed on the surface of a base material and heated to form a polymer layer containing the F polymer (hereinafter also referred to as "F layer")
  • the base material layer composed of the base material and the F polymer layer can be formed.
  • a laminate having the layers in this order is obtained.
  • the F layer is preferably formed by placing the present dispersion on the surface of the base material, heating to remove the liquid dispersion medium, and further heating to bake the F polymer. By separating the base material from such a laminate, a sheet containing the F polymer can be obtained.
  • the base material include those similar to those that can be laminated with the sheet described above, and preferred embodiments thereof are also the same.
  • Methods for disposing the present dispersion include a coating method, a droplet discharge method, and a dipping method, with roll coating, knife coating, bar coating, die coating, or spraying being preferred.
  • Heating during removal of the liquid dispersion medium is preferably carried out at 100 to 200° C. for 0.1 to 30 minutes. In this heating, the liquid dispersion medium does not need to be completely removed, but may be removed to the extent that the layer formed by packing the F particles can maintain a self-supporting film. Furthermore, during heating, air may be blown to encourage removal of the liquid dispersion medium by air drying.
  • Heating during firing of the F polymer is preferably carried out at a temperature equal to or higher than the firing temperature of the F polymer, more preferably at 360 to 400°C for 0.1 to 30 minutes.
  • Examples of heating devices for each heating include an oven and a ventilation drying oven.
  • the heat source in the device may be a contact heat source (hot air, hot plate, etc.) or a non-contact heat source (infrared rays, etc.).
  • each heating may be performed under normal pressure or under reduced pressure.
  • the atmosphere in each heating may be an air atmosphere or an inert gas (helium gas, neon gas, argon gas, nitrogen gas, etc.) atmosphere.
  • the F layer is formed through the steps of disposing and heating the dispersion. These steps may be performed once or may be repeated two or more times.
  • the present dispersion may be placed on the surface of the base material and heated to form an F layer, and the present dispersion may be further placed on the surface of the F layer and heated to form a second F layer.
  • the present dispersion liquid may be further placed on the surface and heated to form the F layer.
  • the present dispersion liquid may be disposed on only one surface of the substrate, or may be disposed on both surfaces of the substrate. In the former case, a laminate is obtained that has a base layer and an F layer on one surface of the base layer, and in the latter case, a laminate is obtained that has a base layer and an F layer on both surfaces of the base layer. A laminate is obtained.
  • the laminate include a metal foil and a metal clad laminate having an F layer on at least one surface of the metal foil, a polyimide film and a multilayer film having an F layer on both surfaces of the polyimide film.
  • Preferred ranges of the dielectric constant, dielectric loss tangent, thermal conductivity, linear expansion coefficient, and peel strength between the F layer and the base material layer of the F layer are the dielectric constant, dielectric loss tangent, The preferred ranges are the same as the thermal conductivity, coefficient of linear expansion, and peel strength between the sheet and the base material.
  • the present invention provides a laminate (hereinafter referred to as "this laminate") in which an F layer is formed on both surfaces of a base material, and the F layer, a base material layer composed of the base material, and the F layer are arranged in this order. ).
  • this laminate from the viewpoint of excellent water absorption and electrical properties, the base material contains two types of diamine units derived from 1,4-bis(4-aminophenoxy)benzene and 4,4'-diaminobenzanilide.
  • the thickness of the F layer varies depending on the use of the laminate, but is preferably in the range of 10 to 200 ⁇ m. Further, the thickness of the F layer is preferably 0.1 times or more the thickness of the base material, which is the above-mentioned polyimide film, and the ratio of the thickness of the base material to the total thickness of the F layer is is preferably 90/10 to 10/90.
  • a primer layer may be further included between the F layer and the polyimide film.
  • the dispersion obtained by this method and the present dispersion are useful as materials for imparting insulation, heat resistance, corrosion resistance, chemical resistance, water resistance, impact resistance, and thermal conductivity.
  • the dispersion obtained by this method and the present dispersion are used in printed wiring boards, thermal interface materials, power module substrates, coils used in power devices such as motors, in-vehicle engines, heat exchangers, Vials, syringes, ampoules, medical wires, secondary batteries such as lithium ion batteries, primary batteries such as lithium batteries, radical batteries, solar cells, fuel cells, lithium ion capacitors, hybrid capacitors, capacitors, capacitors (aluminum electrolytic capacitors, tantalum electrolytic capacitors, etc.), electrochromic devices, electrochemical switching devices, electrode binders, electrode separators, and electrodes (positive and negative electrodes).
  • the dispersion obtained by this method and the present dispersion are also useful as adhesives for bonding parts together.
  • the dispersion obtained by this method and the present dispersion can be used for adhesion of ceramic parts, adhesion of metal parts, adhesion of electronic parts such as IC chips, resistors, capacitors, etc. on substrates of semiconductor elements and module parts, It can be used to bond circuit boards and heat sinks, and to bond LED chips to substrates.
  • the dispersion obtained by this method can be used for antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food products, etc. It is useful as industrial products, heat dissipation parts, etc.
  • electric wire coating materials aircraft wires, flat wires, FFC (Flexible flat cable), etc.
  • enamelled wire coating materials used for motors of electric vehicles etc.
  • coating materials for power generation electrical insulating tapes, Insulating tape for oil drilling, oil transportation hoses, hydrogen tanks, materials for printed circuit boards, separation membranes (precision filtration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), electrode binders ( (for lithium secondary batteries, fuel cells, etc.), carrier films for fuel cells, tape base films for semiconductor manufacturing processes (dicing tapes, pickup tapes, etc.), release films for semiconductor molding, liquid crystal antennas, reflectors, transmission lines.
  • separation membranes precision filtration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.
  • electrode binders for lithium secondary batteries, fuel cells, etc.
  • carrier films for fuel cells tape base
  • base films for COF Chip on film
  • electrostatic chucks for semiconductor manufacturing processes electrostatic chucks for display manufacturing processes, copy rolls, furniture, automobile dashboards, covers for home appliances, etc.
  • sliding members load bearings, yaws, etc.
  • tension ropes wear pads, wear strips, tube lamps, Test sockets, wafer guides, centrifugal pump wear parts, chemical and water supply pumps, tools (shovels, files, chisels, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, racket guts, dies, toilet bowls , container covering materials, mounted heat dissipation boards for power devices, heat dissipation members for wireless communication devices, transistors, thyristors, rectifiers, transformers, power MOS FETs,
  • housings for computers and displays housings for computers and displays, materials for electronic devices, interior and exterior of automobiles, sealing materials for processing machines and vacuum ovens that perform heat treatment under low oxygen conditions, plasma processing equipment, etc., processing units such as sputtering and various dry etching equipment, etc.
  • processing units such as sputtering and various dry etching equipment, etc.
  • the dispersion obtained by this method, molded products such as sheets formed from this dispersion, and laminates including this laminate can be used for electronic board materials such as flexible printed wiring boards and rigid printed wiring boards, protective films, etc. It is useful as a heat dissipation board, especially as a heat dissipation board for automobiles.
  • F particle 1 Contains 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units in this order, and carbonyl group-containing groups per 1 ⁇ 10 6 main chain carbon atoms.
  • Liquid composition 1 containing 45% by mass of F particles 1 was prepared by mixing F particles 1, surfactant 1, and water. During preparation, viscosity modifier 1 and ethanol were added respectively, treated with a high-speed dispersion stirrer (Hyper HSPV10 manufactured by Ashizawa Finetech Co., Ltd.) at 1000 rpm for 20 minutes, and then a defoaming machine (manufactured by Ashizawa Finetech Co., Ltd., "Hyper HSPV10”) for 20 minutes.
  • Vacuum degassing treatment was carried out using a "Bubble Buster 400" (manufactured by Co., Ltd.) at a frequency of 40 Hz and a degree of vacuum of -0.1 MPaG. After taking 1.44 ml of liquid composition 1 and diluting it 250 times, the entire amount was measured using a number counting type particle size distribution analyzer (made by Nihon Entegris Co., Ltd., "AccuSizer (registered trademark) A7000APS", LE400 sensor used). ), and the number of coarse particles (particle concentration) with a particle diameter of 60 ⁇ m or more was measured and found to be 4000 particles/ml. Moreover, the liquid density, surface tension, and viscosity of Liquid Composition 1 were 1.32 g/cm 3 , 24 mN/m, and 3000 mPa ⁇ s in this order.
  • liquid composition 1 was put into a wet bead mill device (“Mugenflow 10” manufactured by Ashizawa Finetech Co., Ltd.) equipped with zirconia beads with a diameter of 0.3 mm, and the liquid composition was heated at a bead filling rate of 85%, a mill circumferential speed of 7 m/s, and Bead milling was performed under the conditions of flow rate 4.0 L/min, residence time 1.10 min, and number of passes 4 times, and the resulting processed product was further processed using a defoaming machine (“Bubble Buster 400" manufactured by Ashizawa Finetech Co., Ltd.) ) under the conditions of a frequency of 40 Hz and a degree of vacuum of -0.1 MPaG to obtain a dispersion liquid 1.
  • the dispersion fluidity state of Dispersion Liquid 1 was good, and the number of coarse particles (particle concentration) thereof was measured in the same manner as above and was found to be 100 particles/ml.
  • Example 2 A liquid composition containing 45% by mass of F particles 1 was prepared by mixing F particles 1, surfactant 1, and water in the same manner as in Example 1, except that only viscosity modifier 1 was added.
  • Product 2 was prepared. Further, when the number of coarse particles of liquid composition 2 was measured in the same manner as in Example 1, it was 6000 particles/ml, and the liquid density, surface tension, and viscosity of liquid composition 2 were 1.34 g/cm in this order. 3 , 33 mN/m, and 3000 mPa ⁇ s.
  • a bead mill treatment followed by a vacuum defoaming treatment was performed in the same manner as in Example 1 except that Liquid Composition 2 was used to obtain Dispersion 2.
  • the number of coarse particles (particle concentration) in Dispersion 2 was 800 particles/ml.
  • F particles 1, surfactant 1, and water were mixed in the same manner as in Example 1, except that only ethanol was added, to prepare liquid composition 3 containing 45% by mass of F particles 1. was prepared.
  • the number of coarse particles of liquid composition 3 was 4000 pieces/ml, and the liquid density, surface tension, and viscosity were 1.33 g/cm 3 , 25 mN/m, and 900 mPa ⁇ s in this order.
  • a bead mill treatment followed by a vacuum defoaming treatment was performed in the same manner as in Example 1 except that Liquid Composition 3 was used to obtain Dispersion 3.
  • the number of coarse particles (particle concentration) in Dispersion 3 was 900 particles/ml.
  • Liquid composition 4 containing 25% by mass of F particles 1 was prepared by mixing F particles 1, surfactant 1, and water in the same manner as in Example 1, except that the content of F particles 1 was changed. was prepared. In addition, during preparation, viscosity modifier 1 and ethanol were added. The number of coarse particles in liquid composition 4 was 3000 pieces/ml, and the liquid density, surface tension, and viscosity of liquid composition 4 were 1.17 g/cm 3 , 24 mN/m, and 2500 mPa ⁇ s in this order. . Dispersion 4 was obtained by performing bead mill treatment and subsequent vacuum defoaming treatment in the same manner as in Example 1 except that liquid composition 4 was used. The number of coarse particles (particle concentration) in Dispersion 4 was 3000 particles/ml.
  • dispersion 1 After storing each dispersion at 20°C for 14 days, we visually checked the condition when transferring it to another container. In the case of dispersion 1, the entire amount was transferred without dripping. I was able to liquidate it. In the case of dispersions 2 and 3, dripping occurred, but the entire amount could be transferred. In the case of Dispersion 4, dripping occurred and residual solid content remained in the original container, making it impossible to transfer the entire amount.
  • Example of manufacturing a laminate A bar coater was applied to the surface of a polyimide long film (34 ⁇ m thick) containing 1,4-bis(4-aminophenoxy)benzene and 4,4'-diaminobenzanilide as diamine-based units. Dispersion 1 obtained in Example 1 above was applied to form a liquid film. Next, the polyimide film on which the liquid film was formed was passed through a drying oven at 120° C. for 5 minutes and dried by heating to obtain a dry film. The dry film was then heated at 380° C. for 3 minutes in a nitrogen oven.
  • Laminate 1 has a polyimide film and polymer layers (thickness: 33 ⁇ m) containing a fused and fired product of F particles 1 on both surfaces thereof.
  • Laminate 2 is made in the same manner except that dispersion 1 is changed to dispersion 2
  • laminate 3 is made in the same manner except that dispersion 1 is changed to dispersion 3
  • dispersion 1 is changed to dispersion 4.
  • Laminated bodies 4 were obtained in the same manner except that. As a result of checking the surface condition of the polymer layer in each laminate, it was found that laminate 1, laminate 2, laminate 3, and laminate 4 had the least amount of streaks and cracks in this order.
  • the dispersion obtained by this method has excellent dispersion stability and ease of handling. Further, it is possible to form a molded product that exhibits the physical properties of the F polymer to a high degree and has particularly excellent surface appearance, specifically, a laminate having a polymer layer formed from the dispersion.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne une dispersion liquide contenant un polymère à base de tétrafluoroéthylène qui présente d'excellentes propriétés physiques telles que sa résistance à la chaleur, ses caractéristiques électriques (faible coefficient de dilatation linéaire, faible constante diélectrique et faible facteur de pertes diélectriques), ou similaire, qui permet de former un article moulé excellent en termes d'apparence superficielle, tout particulièrement en termes de douceur de surface, ou similaire, qui inhibe la formation de particules grossières et présente d'excellentes propriétés de stabilité de dispersion et de manipulation. L'invention concerne également un procédé de fabrication de cette dispersion liquide.　Selon le procédé de fabrication de dispersion liquide de l'invention, une dispersion liquide qui contient des particules de polymère à base de tétrafluoroéthylène, est obtenue par traitement d'une composition liquide de densité de liquide comprise entre １,１５ et １,５ｇ／ｃｍ３ et contenant lesdites particules de polymère à base de tétrafluoroéthylène et un milieu de dispersion liquide à l'aide d'un broyeur à bille par voie humide.
PCT/JP2023/015140 2022-06-10 2023-04-14 Dispersion liquide ainsi que procédé de fabrication de celle-ci, et procédé de fabrication de stratifié WO2023238506A1 (fr)

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